Fluoropolymer alloys

ABSTRACT

This invention relates to fluoropolymer alloys made of melt fabricatable extra-high-molecular weight fluorinated ethylene-propylene copolymer (EHMW-FEP) and one or more other polymers. In fluoropolymer alloys made of EHMW-FEP and polytetrafluoroethylene, weight percentage of the former is 0.1-99.9% and the latter is 99.9-0.1%. The processes for preparing fluoropolymer alloys are blend of dried powder co-mill or wetted powder co-mill. Using the fluoropolymer alloys of this invention, various kinds of articles have been fabricated by melt compression or cold compaction and sintering. These properly fabricated articles show a great improvement in creep property and also a prolonged service life in comparison with those made from ordinary polytetrafluoroethylene.

This is a continuation of application Ser. No. 07/166,094 filed on Mar. 9, 1988, now abandoned, which is a divisional of application Ser. No. 06/843,089 filed on Mar. 24, 1986, now U.S. Pat. No. 4,749,752.

This invention relates to fluoropolymer alloys made of melt fabricatable extra-high-molecular weight fluorinated ethylene-propylene copolymer (EHMW-FEP) and one or more other polymers, their preparation and application.

The fluoropolymer alloys are new materials having different properties different from the original polymers of which they are made. The fluoropolymers provide an important way to prepare new materials with a great variety of properties, because it permits using available polymers, simple process, and short research period. They have interest recently in Sato Kawa, plastics (Japan), 32, 69 (1981). The fluoropolymer alloys which have been reported are limited to blending alloys based on polyvinylidene fluoride, polytetrafluoroethylene (PTFE) dispersions and fluorinated ethylene-propylene copolymer (FEP) dispersion (B.P. 935, 706, (1960); Japanese patent kokai 12521/62.

Polytetrafluoroethylene, "King of plastics", has excellent comprehesive properties. It has excellent thermal and chemical stability, and outstanding electrical insulation and anti-stick properties. But it cannot be fabricated by melt processing, it can only be fabricated by cold compaction and then sintering. Furthermore, its creep-resistance is low. Therefore, its applications are limited.

A fluorinated ethylene-propylene copolymer which has good creep-resistance is a copolymer of tetrafluoroethylene and hexafluoro-propylene, as it can be melt fabricated, due to the presence of trifluoromethyl in the copolymer chain. The chemical inertness and outstanding electrical insulating properties of the copolymer are similar to polytetrafluoroethylene, but its thermal stability is not as good as PTFE, as it can only withstand temperatures up to 200 C., and its cost is higher than that of PTFE.

The purpose of the present invention is to prepare a fluorine-containing material with better properties by blending PTFE and FEP, and obtaining a polymer alloy with excellent properties and which overcomes the drawbacks of the two original polymers.

Processes for preparing polymer alloys made of polytetrfluoroethylene and fluorinated ethylene-propylene copolymer are indicated in B.P. 935, 706 (1960) and Japanese patent kokai 12521/62, by using co-precipitation of these two fluoropolymer dispersions. The processes are complicated and expensive the cost increased. The mechanical properties of the fluoropolymer alloy are worse than that of PTFE and FEP. For example their tensile strength is much lower than that of the two original polymers and only 142-213 Kg/cm² at room temperature.

An important problem is properly matching the polytetrafluoroethylene with a fluorinated ethylene-propylene copolymer in order to get a good fluoropolymer alloy made of PTFE and FEP. These two raw fluoropolymers have different processing temperatures and different thermal stability. The temperature of melt compression molding of FEP is about 310° C., the sintering temperature after cold compaction of PTFE is about 380° C. The decomposition rate of FEP is much higher than that of PTFE at 380° C. Particularly, when FEP resins having carboxyl end group is prepared by copolymerization using persulfates as initiators, it must be roasted at 380° C. in order to stabilize the end group. However, FEP resins become "bread ruck", after roasted, and cannot be blended with PTFE powder.

Another important problem resides in the blend process of preparing a polymer alloy made of PTFE and FEP. In general blending polymers can be carried out by the solution blend, melt blend or dispersion co-precipitate blend methods. As there is no solvent found for PTFE and FEP, they could not be carried out by solution blend. They could not be carried out by melt blend also, because PTFE cannot be melt processed. Therefore, dispersion co-precipitating blend has been the way used in B.P. 935, 706 and Japanese patent kokai 12521/62, although the cost of the polymer alloy is high, as one must use expensive fluorine-containing emulsifiers in preparing dispersion of PTFE and FEP. Besides, the process blend of co-precipitating is rather complicated.

The present invention provides a fluoropolymer alloy made of extra-high-molecular weight fluorinated ethylene-propylene copolymer as its chief component. The EHMW-FEP is characterised by having melt processing property and matching with PTFE.

This also provides a blend process of dried powder co-mill or wetted powder co-mill for preparing the fluoropolymer alloy.

The present invention also provides a fluoropolymer alloy which is characterised by having melt fabrication properties like FEP, and cold compression and sintering properties like PTFE, and having the excellent properties possessed by both PTFE and FEP.

The fourth present invention also provides a series of fluoropolymer alloys made of EHMW-FEP as their chief component, and at least one other polymer (including fluorine-containing or common polymers).

According to the present invention, the EHMW-FEP is a molding powder which can be melt fabricated, with melt viscosity of 1×10⁶ poises or more, a melt flow index less than 0.8 gram/10 min., 12 to 30% by weight of hexafluoropropylene, a weight-average molecular weight of 2×10⁵ or more and a tensile strength of 270 Kg/cm² or more under room temperature.

The process for preparing extra-high-molecular weight fluorinated ethylene-propylene copolymers which can be melt fabricated involves a solution precipitating polymerization with liquid hexafluoropropylene as a solvent, including raising the concentrations of monomers in the reaction area by increasing the amount of monomers in a autoclave and increasing the amount of tetrafluoroethylene in the initial monomer mixture of tetrafluoroethylene and hexafluoropropylene, and reducing the concentration of free radicals in the polymerization area and thus reducing the termination possibility of the copolymer chain by reducing the amount of initiator diisopropyl peroxydicarbonate used. All these conditions are advantageous to growing the copolymer chain and to preparing very high molecular weight copolymers. The polymerization conditions are as follows: 1) charging 0.2-0.5 gram/ml of a mixture of tetrafluoroethylene and hexafluoropropylene in a autoclave, 2) the weight ratio of tetrafluoroethylene in the initial monomer mixture of tetrafluoroethylene and hexafluoropropylene is 11-50%, 3) the percentage of initiator diisopropyl peroxydicarbonate (IPP) is 0.001 to 0.05% equivalents based on monomers, 4) the weight ratio of water and monomer is 3/1 to 1/1; the polymerization temperature is 40°-80° C., is the polymerization pressure is 20-30 Kg/cm² ; and the polymerization time, is 1-5 hours per batch.

According to the present invention, the PTFE used is a commercial resin, including resins prepared by suspension or dispersion polymerization, and have a tensile strength of greater than 270 Kg/cm² at room temperature.

According to the present invention, the other commercal polymers, such as polychlorotrifluoroethylene, polyviny-lidene fluoride, tetrafluoroethylene-ethylene copolymer, polyethylene, polypropylene, polysulfone, polyimide, polycarbonate, polyphenylene oxide, poly (phenylene sulfide) et al, can be used to prepare fluoropolymer alloys together with extra-high-molecular weight fluorinated ethylene-propylene copolymers.

A given weight ratio of EHMW-FEP and one or more other polymers as described above, were ground by mill, separately, and then mixed and ground again until the two or more phases were thoroughly mixed. The mixture passes through a 40-80 mesh and ready for processing.

The mixing and grinding process of two or more polymers may be carried out either in dried powder form or wet powder. During wet powder mixing and grinding, the polymers are moistened by water, ethyl alcohol, ethyl acetate or a mixture of these solvents. When the mixing is finished, the mixture of polymers must be dried, and then screened.

In the fluoropolymer alloy made of EHMW-FEP and PTFE, the weight of EHMW-FEP is 0.1-99.9% and the weight of PTFE is 99.9-0.1%. In a preferred embodiment the alloys contain 0.1-60% of EHMW-FEP and 40-99.9% of PTFE.

The fluoropolymer alloys made of EHMW-FEP and PTFE can be melt pressed into articles at temperatures 300°-350° C. and pressures of 50-200 Kg/cm² like FEP. They can also be cold compressed at a pressure of 50-200 Kg/cm² and then sintered at a temperature of 300°-390° C. like PTFE.

The temperatures of melt pressing or sintering of the fluoropolymer alloys described above depend on the amount of PTFE content. The higher their PTFE, the higher the processing temperature.

The fluoropolymer alloys made of the EHMW-FEP and PTFE of present invention not only have a creep-resistance like FEP, but also high tensile strength under high temperature like PTFE. This exhibits tensile strength of 200-400 Kg/cm² and elongation of 300-700% at room temperature, and correspondingly 50-200 Kg/cm² and 300-700% at 200° C. This extra-high-molecular weight fluorinated ethylene-propylene copolymers is compatible with polytetrafluoroethylene in the fluoropolymer alloys described above. Fluoropolymer alloys, made e.g. of 10% of EHMW-FEP and 90% of PTFE, have only one melting peak and one peak of crystallizing in its DSC spectrum.

All kinds of fluoropolymer alloys described above can be reinforced and improved by adding glass fibers, graphite, molybdenum disulfide, carbon and various metal powders.

The fluoropolymer alloys made EHMW-FEP and PTFE of present invention have excellent thermal stability, chemical inertness and outstanding electrical insulating properties. Using this kind of fluoropolymer alloys material, various diaphragm, seals, lining valves, lining pipes, lining pump, various components of pump, such as shell, wheel, wind wrap wire etc. can be fabricated. The articles made of fluoropolymer alloys have better creep-resistance than that of PTFE and consequently have a rather long operating life.

The fluoropolymer alloys described above can be used in power coating by either the electrostatic or flow-bed method, and can also be fabricated into complex articles using ram-extruding a paste consisting of fluoropolymer alloy and petroleum ether or kerosene.

The invention is more specifically described and explained by means of the following examples which, however, are not intended to be limiting. In the examples all parts and percentages are by weight except as otherwise noted.

EXAMPLE 1

20 grams of EHMW-FEP melt flow index of 0 gram/10 min., and 180 grams PTFE have successively been moistened by a mixture of ethyl alcohol and ethyl acetate, milled, filtered, dried and passed through a 40 mesh screen. The resulting powder is cold compressed into a 2 mm thick sheet under pressure of 80 Kg/cm², and sintered in a over for 1 hour at 350° C. After cooling, its tensile strength is 277 Kg/cm² under room temperature.

EXAMPLE 2

EHMW-FEP is mixed with PTFE in the weight ratio of 1/9, 1/3, 1/1, 3/1 and 9/1 respectively. The resulting mixtures are milled to pass through a 40 mesh screen, cold compressed under 80 Kg/cm² and sintered separately. The properties of the resulting fluoropolymer alloys are shown in Table 1.

                  TABLE 1                                                          ______________________________________                                         Physical properties of alloys made of EHMW-                                    FEP/PTFE                                                                       ______________________________________                                         Composition 1/0    9/1    3/1  1/1  1/3  1/9  0/1                              (EHMW-FEP/                                                                     PTFE)                                                                          sintering temp. (°C.)                                                               300    300    300  320  340- 340- 365                                                                  365  365                                   room tensile                                                                               265    210    250  290  260  280  320                              strength temp.                                                                 (Kg/cm.sup.2)                                                                  elongation (%)                                                                             330    310    370  500  520  520  650                              200° C. tensile                                                                      46     87     84   82   89  104   89                              strength (Kg/cm.sup.2)                                                         elongation (%)                                                                             340    340    500  450  500  680  480                              ______________________________________                                    

EXAMPLE 3

Mixing EHMW-FEP with tetrafluoroethylene-ethylene copolymer (F40) in weight ratio showed in Table 2 by blending dried powder or wetted powder, the resulting fluoropolymer alloys are fabricated by cold compression at a pressure of 70-150 Kg/cm² and then sintered, or melt pressed.

                                      TABLE 2                                      __________________________________________________________________________     Physical properties of alloys made of EHMW-                                    FEP and F40                                                                    __________________________________________________________________________     Composition                                                                              1/0                                                                               99/1                                                                              9/1                                                                               3/1                                                                               1/1                                                                               1/3                                                                               1/9                                                                               1/99                                                                              0/1                                          (EHMW-FEP/F40)                                                                 fabrication                                                                              310-                                                                              300-                                                                              300-                                                                              300-                                                                              300-                                                                              300-                                                                              300-                                                                              280-                                                                              280-                                         temp. (°C.)                                                                       380                                                                               350                                                                               340                                                                               330                                                                               320                                                                               320                                                                               320                                                                               330                                                                               340                                          tensile   300                                                                               310                                                                               315                                                                               320                                                                               325                                                                               330                                                                               340                                                                               350                                                                               400                                          strength                                                                       (Kg/cm.sup.2)                                                                  elongation                                                                               300                                                                               300                                                                               280                                                                               260                                                                               200                                                                               150                                                                               100                                                                               100                                                                               100                                          (%)                                                                            __________________________________________________________________________

EXAMPLE 4

A mixture of 40 grams of EHMW-FEP, 40 grams of PTFE and 10 grams of polysulfone, is moistened with acetone, mixed homogeneously by high speed stirring, milled, dried, 40 mesh screened, cold compressed under 80 Kg/cm² and then sintered for one hour at 320° C. The hardness (Rockwell) of the fluoropolymer alloy obtained is D50.

EXAMPLE 5

EHMW-FEP is mixed with polychlorotrifluoroethylene (CTFE) in the weight ratio shown in Table 3 by blending dried powder or wetted powder, the resulting fluoropolymer alloys are fabricated by cold compression at a pressure of 70-150 Kg/cm² and then sintering, or by melt pressing.

                                      TABLE 3                                      __________________________________________________________________________     Physical properties of alloys made of EHMW-                                    FEP and CTFE                                                                   __________________________________________________________________________     Composition 1/0                                                                               99/1                                                                              9/1                                                                               3/1                                                                               1/1                                                                               1/3                                                                               1/9                                                                               1/99                                                                              0/1                                        (EHMW-FEP/CTFE)                                                                fabrication 310-                                                                              310-                                                                              300-                                                                              270-                                                                              250-                                                                              250-                                                                              250-                                                                              250-                                                                              250-                                       temp. (°C.)                                                                         380                                                                               330                                                                               330                                                                               300                                                                               300                                                                               300                                                                               300                                                                               300                                                                               320                                        tensile strength                                                                           300                                                                               280                                                                               200                                                                               220                                                                               300                                                                               305                                                                               320                                                                               300                                                                               350                                        (Kg/cm.sup.2)                                                                  elongation (%)                                                                             350                                                                               300                                                                                40                                                                               100                                                                               250                                                                               180                                                                               200                                                                               150                                                                               150                                        __________________________________________________________________________

EXAMPLE 6

EHMW-FEP is mixed with polyvinylidene fluoride (PVDF) in weight ratios shown in Table 4 by blending dried powder or wetted powder (using diisobutyl acetone as a moistener). The resulting fluoropolymer alloys are fabricated by cold compression at a pressure of 70-150 Kg/cm² and then sintering, or by melt pressing.

                                      TABLE 4                                      __________________________________________________________________________     Physical properties of alloys made of EHMW-                                    FEP and PVDF                                                                   __________________________________________________________________________     Composition 1/0                                                                               99/1                                                                              9/1                                                                               3/1                                                                               1/1                                                                               1/3                                                                               1/9                                                                               1/99                                                                              0/1                                        (EHMW-FEP/PVDF)                                                                fabrication 310-                                                                              280-                                                                              280-                                                                              280-                                                                              250-                                                                              240-                                                                              220-                                                                              200-                                                                              200-                                       temp. (°C.)                                                                         380                                                                               320                                                                               330                                                                               330                                                                               330                                                                               300                                                                               250                                                                               250                                                                               250                                        tensile strength                                                                           310                                                                               330                                                                               350                                                                               300                                                                               300                                                                               350                                                                               400                                                                               450                                                                               500                                        (Kg/cm.sup.2)                                                                  elongation (%)                                                                             320                                                                               250                                                                               200                                                                               150                                                                               150                                                                               100                                                                                60                                                                                60                                                                                50                                        __________________________________________________________________________

EXAMPLE 7

EHMW-FEP is mixed with polysulfone (PS) in weight ratios shown in Table 5 by blending dried powder or wetted powder (including using chloroform as a solvent), the resulting flyoropolymer alloys are fabricated by melt compression under pressure of 70-150 Kg/cm².

                                      TABLE 5                                      __________________________________________________________________________     Physical properties of alloys made of EHMW-                                    FEP and PS                                                                     __________________________________________________________________________     Composition                                                                              1/0                                                                               99/1                                                                              9/1                                                                               3/1                                                                               1/1                                                                               1/3                                                                               1/9                                                                               1/99                                                                              0/1                                          (EHMW-FEP/PS)                                                                  fabrication                                                                              310-                                                                              280-                                                                              250-                                                                              220-                                                                              250-                                                                              250-                                                                              270-                                                                              200-                                                                              200-                                         temp. (°C.)                                                                       380                                                                               320                                                                               310                                                                               300                                                                               290                                                                               290                                                                               280                                                                               270                                                                               280                                          tensile   300                                                                               270                                                                               250                                                                               220                                                                               200                                                                               250                                                                               360                                                                               700                                                                               800                                          strength                                                                       (Kg/cm.sup.2)                                                                  elongation                                                                               320                                                                               250                                                                               200                                                                               100                                                                                4  5  5  40                                                                                50                                          (%)                                                                            __________________________________________________________________________

EXAMPLE 8

EHMW-FEP is mixed with polyethylene (PE) in the weight ratios shown in Table 6 by blending dried powder or wetted powder (using xylene as a solvent). The resulting fluoropolymer alloys are fabricated by melt compression at a pressure of 70-150 Kg/cm².

                                      TABLE 6                                      __________________________________________________________________________     Physical properties of alloys made of EHMW-                                    FEP and PE                                                                     __________________________________________________________________________     Composition                                                                              1/0                                                                               99/1                                                                              9/1                                                                               3/1                                                                               1/1                                                                               1/3                                                                               1/9                                                                               1/99                                                                              0/1                                          (EHMW-FEP/PE)                                                                  fabrication                                                                              310-                                                                              280-                                                                              250-                                                                              200-                                                                              170-                                                                              150-                                                                              160-                                                                              150-                                                                              150-                                         temp. (°C.)                                                                       380                                                                               350                                                                               300                                                                               300                                                                               250                                                                               200                                                                               170                                                                               170                                                                               200                                          tensile strength                                                                         300                                                                               280                                                                               250                                                                               180                                                                               100                                                                               150                                                                               190                                                                               200                                                                               200                                          (Kg/cm.sup.2)                                                                  elongation 1%                                                                            350                                                                               300                                                                               200                                                                               100                                                                                50                                                                               400                                                                               600                                                                               210                                                                               250                                          __________________________________________________________________________

EXAMPLE 9

EHMW-FEP is mixed with polypropylene (pp) in the weight ratios shown in Table 7 by blending dried powder or wetted powder (using decalin as a solvent). The resulting fluoropolymer alloys are fabricated by melt compression under pressure of 70-150 Kg/cm².

                                      TABLE 7                                      __________________________________________________________________________     Physical properties of alloys made of EHMW-                                    FEP and PP                                                                     __________________________________________________________________________     Composition                                                                              1/0                                                                               99/1                                                                              9/1                                                                               3/1                                                                               1/1                                                                               1/3                                                                               1/9                                                                               1/99                                                                              0/1                                          (EHMW-FEP/PP)                                                                  fabrication                                                                              310-                                                                              300-                                                                              280-                                                                              250-                                                                              230-                                                                              220-                                                                              220-                                                                              220-                                                                              230-                                         temp. (°C.)                                                                       380                                                                               330                                                                               320                                                                               300                                                                               300                                                                               280                                                                               250                                                                               260                                                                               300                                          tensile strength                                                                         310                                                                               300                                                                               280                                                                               200                                                                               180                                                                               200                                                                               240                                                                               310                                                                               350                                          (Kg/cm.sup.2)                                                                  elongation (%)                                                                           340                                                                               300                                                                               350                                                                               200                                                                               300                                                                               350                                                                               500                                                                               250                                                                               200                                          __________________________________________________________________________

EXAMPLE 10

EHMW-FEP is mixed with polycarbonate (PC) in the weight ratios shown in Table 8 by blending dried powder or wetted powder (using chloroform as a solvent). The resulting fluoropolymer alloys are fabricated by melt compression at a pressure of 70-150 Kg/cm².

                                      TABLE 8                                      __________________________________________________________________________     Physical properties of alloys made of EHMW-                                    FEP and PC                                                                     __________________________________________________________________________     Composition                                                                              1/0                                                                               99/1                                                                              9/1                                                                               3/1                                                                               1/1                                                                               1/3                                                                               1/9                                                                               1/99                                                                              0/1                                          (EHMW-FEP/PC)                                                                  fabrication                                                                              310-                                                                              300-                                                                              290-                                                                              290-                                                                              280-                                                                              280-                                                                              280-                                                                              250-                                                                              220-                                         temp. (°C.)                                                                       380                                                                               350                                                                               340                                                                               330                                                                               320                                                                               310                                                                               310                                                                               320                                                                               350                                          tensile strength                                                                         310                                                                               300                                                                               280                                                                               260                                                                               200                                                                               300                                                                               360                                                                               550                                                                               700                                          (Kg/cm.sup.2)                                                                  elongation (%)                                                                           350                                                                               300                                                                               200                                                                               100                                                                                50                                                                                10                                                                                5  80                                                                               100                                          __________________________________________________________________________

EXAMPLE 11

EHMW-FEP is mixed with polyphenylene oxide (ppo) in the weight ratios shown in Table 9 by blending dried powder or wetted powder (using chloroform as a solvent). The resulting fluoropolymer alloys are fabricated by melt compression at a pressure of 70-150 Kg/cm².

                                      TABLE 9                                      __________________________________________________________________________     Physical properties of alloys made of EHMW-                                    FEP and PPO                                                                    __________________________________________________________________________     Composition                                                                              1/0                                                                               99/1                                                                              9/1                                                                               3/1                                                                               1/1                                                                               1/3                                                                               1/9                                                                               1/99                                                                              0/1                                          (EHMW-FEP/                                                                     PPO)                                                                           fabrication                                                                              310-                                                                              300-                                                                              300-                                                                              300-                                                                              300-                                                                              300-                                                                              305-                                                                              300-                                                                              300-                                         temp. (°C.)                                                                       380                                                                               320                                                                               320                                                                               320                                                                               320                                                                               320                                                                               310                                                                               320                                                                               350                                          tensile strength                                                                         305                                                                               280                                                                               250                                                                               200                                                                               150                                                                                50                                                                               110                                                                               250                                                                               650                                          (Kg/cm.sup.2)                                                                  elongation (%)                                                                           330                                                                               250                                                                               200                                                                               100                                                                                10                                                                                4  5  40                                                                                50                                          __________________________________________________________________________

EXAMPLE 12

EHMW-FEP is mixed with polyphenylene sulfide (PPS) in the weight ratios shown in Table 10 by blending dried or wetted powder. The resulting fluoropolymer alloys are fabricated by melt compression at a pressure of 70-150 Kg/cm².

                                      TABLE 10                                     __________________________________________________________________________     Physical properties of alloys made of EHMW-                                    FEP and PPS                                                                    __________________________________________________________________________     Composition                                                                              1/0                                                                               99/1                                                                              9/1                                                                               3/1                                                                               1/1                                                                               1/3                                                                               1/9                                                                               1/99                                                                              0/1                                          (EHMW-FEP/PPS)                                                                 fabrication                                                                              310-                                                                              300-                                                                              300-                                                                              300-                                                                              300-                                                                              300-                                                                              300-                                                                              300-                                                                              290-                                         temp. (°C.)                                                                       380                                                                               350                                                                               350                                                                               350                                                                               350                                                                               350                                                                               350                                                                               350                                                                               360                                          tensile strength                                                                         300                                                                               290                                                                               280                                                                               250                                                                               200                                                                               300                                                                               400                                                                               850                                                                               900                                          (Kg/cm.sup.2)                                                                  elongation (%)                                                                           320                                                                               300                                                                               250                                                                               200                                                                               100                                                                                50                                                                                5  15                                                                                10                                          __________________________________________________________________________

EXAMPLE 13

EHMW-FEP is mixed with polyimide (PI) in the weight ratios shown in Table 11 by blending dried powder or wetted powder. The resulting fluoropolymer alloys are fabricated by melt compression under pressare of 70-150 Kg/cm² or cold compaction at a pressure of 70-150 Kg/cm² and sintering.

                                      TABLE 11                                     __________________________________________________________________________     Physical properties of alloys made of EHMW-                                    FEP and PI                                                                     __________________________________________________________________________     Composition                                                                              1/0                                                                               99/1                                                                              9/1                                                                               3/1                                                                               1/1                                                                               1/3                                                                               1/9                                                                               1/99                                                                              0/1                                          (EHMW-FEP-PI)                                                                  fabrication                                                                              310-                                                                              300-                                                                              300-                                                                              300-                                                                              300-                                                                              300-                                                                              310-                                                                              250-                                                                              150-                                         temp. (°C.)                                                                       380                                                                               320                                                                               320                                                                               320                                                                               320                                                                               320                                                                               320                                                                               300                                                                               300                                          tensile strength                                                                         320                                                                               310                                                                               300                                                                               250                                                                               200                                                                               300                                                                               400                                                                               800                                                                               900                                          (Kg/cm.sup.2)                                                                  elongation (%)                                                                           330                                                                               300                                                                               280                                                                               250                                                                               100                                                                                80                                                                                50                                                                                10                                                                                5                                           __________________________________________________________________________

EXAMPLE 14

10 grams of EHMW-FEP are mixed with 90 grams of molding or dispersion powder of PTFE, the resulting mixture was milled, and 40 mesh screened. The resulting dried powder of fluoropolymer alloy are moistened with 200C gasoline, cold compressed and sintered. This fluoropolymer alloy product can be used for lining valves and pipes.

EXAMPLE 15

40 grams of fluoropolymer alloy made of EHMW-FEP are mixed with PTFE with glass fiber in the weight percentage of 10%, 20% and 30% respectively. The resulting mixture is cold compressed under pressure of 80 Kg/cm² and sintered for 2 hours at 320° C. separatly. The tensile strength of these reinforced fluoropolymer alloy is 250, 220 and 150 Kg/cm², respectively, at room temperature.

EXAMPLE 16

A fluoropolymer alloy made of 50 grams of EHMW-FEP and 50 grams of PTFE with glass fiber in a weight percentage of 20% and graphite in its weight ratio of 3%, the resulting mixture is milled to pass through 40 mesh screen, cold compressed under pressure of 80 Kg/cm² and then sintered for 2 hours at 320° C. The tensile strength, elongation and hardness (Rockwell) of the reinforced fluoropolymers alloys are 150 Kg/cm², 220% and 58, respectively.

EXAMPLE 17

Process for preparing extra-high-molecular weight fluorinated ethylene-propylene copolymer, e.g. in a stainless-steel autoclave having a capacity of 130 liters are charged 60 liters of deionized water, 45 Kg of initial monomers containing 86.6% hexafluoropropylene. The contents are heated to 55°-57° C. at a pressure of 22.0 Kg/cm², then 25 ml of diisopropyl peroxydicarbonate are added. The copolymerization is carried on for three hours. 7.5 Kg of dried copolymer powder having a hexafluoropropylene weight ratio of 14.5%, a melt viscosity of 1.8×10⁶ poises and a melt flow index of 0.3 g/10 min could been obtained. A sample of the copolymer powder is molded into sheet with a thickness of 2 mm at 310° C., which shows the tensil strength 290 Kg/cm² elongation 320%; and flex fatigue life more than 2×10⁵ cycle under room temperature. 

What we claim is:
 1. An extra-high-molecular weight tetrafluoroethylene hexafluoropropylene copolymer which is melt fabricatable comprising a hexafluoropropylene content of 12-30% by weight, a weight-average molecular weight of over 2.1×10⁵, a melt viscosity higher than 1.5×10⁶ poises, and a melt flow index less than 0.8 gram/10 minutes. 